H-FAME

Introduction of H-FAME Technology
H-FAM E
(Partially Hydrogenated FAM E) :
New alternative biodiesel superior
in ox idation and therm al stabilities,
and produced after the partial
hydrogenation of the current FAM E.
H-FAM E is m onoene-rich FAM E.
Dr. Yuji YOSHIMURA
Leader/Research Director of Thailand-Japan SATREPS Project,
National Institute of Advanced Industrial Science and Technology
(AIST), Japan
Dr. Paritud BHANDHUBANYONG
Project Director of Thailand-Japan SATREPS Project,
Panyapiwat Institute of Management (PIM) -TISTR, Thailand
WS on higher blending of biodiesel (17-18, September 2015 @Bangkok)
1
H-FAME from Thailand-Japan collaboration
H-FAME technology is developed
through
Thailand-Japan collaboration SATREPS PJ of
“Innovation on production and automotive utilization
of biofuels from non-food biomass” (FY2010-FY2015)
Japan
Kingdom of
Thailand
KMUTNB
Japan Science
and Technology
Agency
Science and Technology
Research Partnership for
Sustainable Development
Japan
International
Cooperation
Agency
• National Institute of Advanced Industrial Science and Technology (AIST)
• Waseda University
• National Science and Technology Development Agency (NSTDA)
•Thailand Institute of Science and Technological Research (TISTR)
•King Mongkut’s University of Technology NB
2
Contents
1. Background and motivation
2. What is H-HAME ? How to produce H-FAME ?
P artially Hydrogenated FAM E (H-FAM E) as a new
alternative biodiesel
3. Properties and advantages of H-FAME
4. Feasibility of H-FAME
5. On-road durability tests by using B20 fuel blended
with Palm H-FAME
6. Future plan for H-FAME technology
7. Conclusions
3
1. Background: Importance of quality assurance
FAME as an alternative fuel, and used as a diesel blend stock,
but easy to be oxidized…..
Bx
Fresh B100,
and Bx
Storage/delivery
Quality assurance
Vehicle use
Low er blending Bx can be used safely
in vehicles, if Bx quality is assured.
Thai standard,
B100,
Bx
(EEBS):2008 WWFC
Bx: X vol %
 B100 spec for B5, B7,
FAME and
etc., e.g., 1,000 ppm
(100-x) vol %
petrodiesel
BHT in B100 for B7.
 Bx (FAME blended
diesel) spec..
 Antioxidants will retard
oxidative degradation of
polyunsaturated FAME.
4
Increased cautions for the higher FAME blending
With increasing the FAME blending ratio, …
Bx
Storage/ delivery
Low
Oxidation stability
High
Fresh B100, and Bx
Vehicle use
Will cause several damages
on engine systems.
enough AO
Minimum level of quality
 More degradation of FAME in fuel
station, fuel tank, engine oil pan, etc.
e.g., engine oil sludging
via. expirering of antioxidants, metals
due to biodiesel aging
contaminants assisted oxidation,
in engine oil
inappropriate handling/storage, etc.
Storage time/oxidation severity
(Mercedes-Benz
Biodiesel Brochure)
5
1-2. Key compounds for FAME upgrading
OCH3
<Oxidative degradation issue>
O
FAME is mixtures of several types of fatty acid
methyl esters, and polyunsaturated FAMEs are key
components to determine the oxidative/thermal
stabilities of FAME.
O OCH3
O
O
<Precipitation/filter plugging issues>
HO
Not yet standardized in FAME specifications, but ..
HO
Saturated monoglyceride (SMG) will precipitate
even at higher temperature than cloud point,
mainly after blending of FAME with petrodiesel (Bx).
Sterol glucoside (SG) will
Precipitate during the storage
of FAME, mainly for B100 FAME.
6
1-3. Properties of unsaturated FAME molecules
e.g.,
C18:n FAME
molecule
OCH3
C18:3
Oxidation Peroxide Cold flow Solvency
stability formation property
effect
Acid
corrosion,
Elastomer
filter
cleaning
polymers
damage plugging
effect
and sludge
formation
(98*)
✕✕
✕✕
◎◎
○
✕
✕
◎
○
○
○
○
○
◎
✕
○
O
C18:2
OCH3
(41)
O
C18:1
OCH3
O
C18:0
OCH3
(1)
(<1)
◎
O
Methyl ester group
• Ease of oxidation:
E.N. Frankel, Lipid Oxidation, 2005
M onoene (m onounsaturated FAM E) seem s to be reliable com ponent.
7
2. What is H-FAME ?
H-FAM E (P artially Hydrogenated FAM E) : New alternative biodiesel
superior in ox idation and therm al stabilities, and produced after
the partial hydrogenation of the current FAM E. H-FAM E is m onoene
(m onounsaturated FAM E)-rich FAM E.
Hydrogen
FAME
T<140 ºC
P<0.5 MPa
H-FAME
Hydrogenation catalysts
FAME + Hydrogen = H-FAME
e.g., C18:n FAME molecule
C18:3
OCH3
But, partial
hydrogenation !
Degree of hydrogenation
O
OCH3
C18:2
O
C18:1
Partial
hydrogenation
OCH3
O
C18:0
OCH3
O
Complete
hydrogenation
8
2-1. How to produce the H-FAME ?
< B5-B7
antioxidant
Current biodiesel production process
Conventional
FAME
MeOH Catalyst(H2SO4/KOH)
H2 Catalyst
Vegetable
/Plant oils,
etc.
Esterification
/Transesterification
FAME
Partial
hydrogenation
< B10-B20
H-FAME
 Incidental facility
Glycerin
H2 Catalyst
Hydrodeoxy
-genation
H2 Catalyst
Gas
(C3H8, H2O,
CO2, CO, etc.)
Isomerization
Gasoline
H-FAM E is a friendly
fuel to the current
biodiesel com panies:  High-pressure and high-temperature
P <0.5M P a, T<140 ºC
facility (e.g., P>5 MPa, T>280 ºC)
HVO,BHD
 Large plant size to get a scale merit
 Very high hydrogen consumption
9
Comparison between H-FAME and HVO/BHD
BHD/HVO
H-FAME
O
O
Main reaction
OCH3
O
O
OCH3
O
OCH3
O
Mono/Polyunsaturated FAME
OCH3
O
Monounsaturated FAME
Oil (Triglyceride)
O
O
O
Hydrocarbons
Hydrogen
consumption
Partial hydrogenation : 3H2
Hydrogenolysis/hydrogenation
: 18H2
Decarboxylation: 9H2
More hydrogen for the
isomerization reaction
Reaction
Conditions
Low pressure
(atmospheric~0.5MPa)
Low temperature (80~140ºC)
High pressure (>5MPa)
High temperature (>280ºC)
10
Oxidation stability of B100 (h)
Production cost for B100
2-2. Positioning of H-FAME in biodiesels
Blending limitation of FAME (B5-B7)
JAMA’s recommendation
80
HVO, BHD, etc.
(Hydrocarbons and not FAME)
60
Very reliable fuel,
but relatively
higher costincrease
40
15
10
5
0
Hydrogen ~0.10.2 wt%/FAME
H-FAME
1st gen.
P alm M E
R apeseed M E
Jatropha M E
Soybean M E
B5
B10
Hydrogen
~3 wt%/VO
Reliable and
affordable fuel
Thai standard of 10 h
Conventional FAME
B15
B20
//
Biodiesel blended with petroleum diesel (Bx*)
*X vol% of biodiesel and (100-X) vol% of petroleum diesel
11
2-3. Palm H-FAME from TISTR’s pilot plant
Conventional
Palm FAME
FAME partial
hydrogenation
PP@TISTR
(100 L/batch),
H-FAME
HYD reaction
conditions:
Temperature:
80 ºC〜140 ºC
 H2 pressure:
< 0.5 MPa
Pd-based catalyst:
12
3. Properties of palm H-FAME (Pilot Plant @TISTR)
Items
Density
Viscosity
Flashpoint
Sulfated ash
Ash content
Water content
Total contamination
Oxidation stability
Iodine value
Monoglyceride content
Trace metals
Cloud point
CFPP
Additive
Saturated
monoglyceride in MG
Sterol glucoside
Units
kg/m3
mm2/s
ºC
mass%
mass%
mg/kg
mg/kg
hrs.
mass%
ºC
ºC
mass%
ppm
Thailand
DOEB 2014
860-900
3.50-5.00
120 min.
0.02 max.
500 max.
24 max.
10 min
120 max.
0.70 max.
Report
Report
Approval
EAS-ERIA BDF Std
(EEBS):2008
860-900
2.00-5.00
100 min.
0.02 max.
500 max.
24 max.
10.0 min. (**)
Reported (*)
0.80 max.
-
WWFC
March, 2009
Report
2.0-5.0
100 min.
0.005 max.
0.001 max.
500 max.
24 max.
10 min.
130 max.
0.80 max.
no addition
-
-
-
-
TISR's PP
H-FAME
872
4.5
168
<0.001
375
1
86.3
42
0.18
16 ºC
16 ºC
0.08
24
EAS: East Asia Summit ; ERIA: Economic Research Institute for ASEAN and East Asia；
WWFC: World Wide Fuel Charter
13
3-1. Advantages of H-FAME and H-FAME process
1. Meets with all of
FAME standards
11. No need of high
pressure facilities and
distillation facilities.
10. Volume-up
reaction
9. Make ease of
metals removal
2. High oxidation stability
(>>10h） (less acids/
corrosion)
3. Less peroxides formation
(more elastomer tolerance)
H-FAME
8. Make ease of sterol
glyceride (SG) removal
4. Decrease in heavier
fraction (less polymerization/ deposits)
5. Increase in
Cetane number
7. Make ease of removal 6. Less sludge formation during
of saturated fatty acid oxidative/thermal degradation
(less deposits)
monoglyceride (SMG)
14
3-2. Less sludge formation via. H-FAME
H-FAM E is very effective to m inim ize
After ox idation,
the sludge form ation !
Depth of Hydrogenation
light
medium
B20
B20 H-FAME B20 H-FAME
Diesel (B0)
Current FAME
(Japanese
Before oxidation,
EURO V diesel) (Thai Palm FAME)
Accelerated oxidation condition:
Bx=20g, T=135 ºC (>115 ºC*),
O2 Flow=100 ml/min,
Oxidation period=16 h.
B0
B20
B20
deep
B20 H-FAME
B20
B20
*Testing condition for oxidation stability in Japanese quality
assurance law for B5 (former method). Now PetroOXY method is used.
15
4. Feasibility of H-FAME (affordability)
1,800
1,800
Production cost of several
biofuels（US$/ton)
1,600
1,600
1,400
1,400
BDF 100,000 t/y
Plant size of 100,000 t/y
Palm FAME
Less cost-up
1,200
1,200
1,000
Petroleum diesel
1,000
800
Diesel price in Thailand
（2011）(
)
 ROI 10%
ROI 10％
 Fixed costs
 Variable固定費
costs
変動費
ROI: Return
on investment
800
600
600
Market price of Palm oil（USCIF)： 800 US$/ton （2010.Apr).
400
400
200
200
0
0
1G-BDF
1st gen.
FAME
(PalmFAME)
1.5G-BDF
H-FAME
(Palm H-FAME)
2G-BDF
HVO
(Palm NExBTL)
Environmental Research Institute,
Waseda University (2011)
3G-BDF
FT-BTL
(BTL)
 Small cost up for H-FAME compared with 1st gen. FAME, but
much less than HVO (BHD), even after newly installation of an
on-site H2 package unit.
 High proportion of variable costs for FAME, H-FAME and HVO. i.e.,
more than 80 % of the total production cost , so reduction of raw
materials costs will be the key to increase its feasibility.
16
5. On-road test by using B20 (Palm H-FAME)
Verification of automotive compatibility of H-FAME, with the
collaboration of Isuzu Thailand group and petroleum company .
Testing fuel of B20: 20 vol % of Palm H-FAME blended with 80 vol %
of Thai petro-diesel.
 Testing periods: Jan.5, 2015 〜 Mar. 2015 (50.000 km).
 Testing vehicle: ISUZU pick up truck, D-MAX Super Daylight (EUROIV)
Isuzu D-Max
Petroleum diesel
(S<50 ppm)
H-FAME
B100, Blending &
property check
Successfully
finished !
Fuel: B20 of
P alm H-FAM E
17
6. Future proposal of demonstration PJ
To confirm the
process m aturity
of H-FAM E
technologies, etc.
Plant capacity :
１0-30 tons of H-FAME
/day (1/10-1/30 in size
of the commercial
FAME plants)
H-FAME plant package
e.g.,
P<0.5 MPa
T<140 ºC
WHSV> 20 h-1
FAME standards
Palm FAME
Palm
H-FAME
Thai standard,
I f w e w ill apply for Japanese NEDO’s I nternational Collaboration Project
Japanese organization
(NEDO)
subsidy
Japanese private sectors,
collaborating with AIST, etc.
MOU
Thai organization
Tentative
ID
Implementation
document
Thai private sectors,
collaborating with
NSTDA/MTEC, TISTR, etc.
18
7. Conclusions
1. Partially hydrogenated FAME (H-FAME) is a
new alternative biodiesel, and can be produced
from any kinds of FAME , e.g., Palm FAME,
Jatropha FAME and Waste cooking oil FAME, etc.
2. H-FAME is a reliable and affordable biodiesel,
and can be used as a nation-wide high-speed
biodiesel blend stock even at the higher
blending use, e.g., up to B20 for Palm H-FAME.
3. H-FAME will support the Thai Alternative
Energy Development Action Plan (AEDP) as one of
the new alternative biodiesels.
19
Acknowledgements
Japan
Kingdom
of Thailand
KMUTNB
We deeply appreciate JST and JICA for their financial supports.
We also deeply thank all of the research participants of NSTDA/MTEC,
TISTR. KMUTNB, WASEDA U. and AIST for their contributions to this Project.
We also deeply thank the ISUZU Thailand group for their kind supports on
the on-road tests, and PTT, Bangchak and Thai oil for supplying the
FAME(B100) and petro diesel (B0) and for measuring the fuel quality.
Thank you for your kind attention
20
The 60th
birthday
21